EP2732001B1 - Procédé de prétraitement de pièces de formage constituées de compositions de matière fibreuse contenant une matrice en matière synthétique et destinées au collage - Google Patents

Procédé de prétraitement de pièces de formage constituées de compositions de matière fibreuse contenant une matrice en matière synthétique et destinées au collage Download PDF

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Publication number
EP2732001B1
EP2732001B1 EP12735288.8A EP12735288A EP2732001B1 EP 2732001 B1 EP2732001 B1 EP 2732001B1 EP 12735288 A EP12735288 A EP 12735288A EP 2732001 B1 EP2732001 B1 EP 2732001B1
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EP
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Prior art keywords
kfz
plastic matrix
polyurethane
polyols
defined region
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EP12735288.8A
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German (de)
English (en)
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EP2732001A1 (fr
Inventor
Martin Linnenbrink
Wolfgang Roock
Florian Ittrich
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Sika Technology AG
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Sika Technology AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
    • C08J5/128—Adhesives without diluent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/22—Presence of unspecified polymer
    • C09J2400/228—Presence of unspecified polymer in the pretreated surface to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin
    • C09J2463/006—Presence of epoxy resin in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin
    • C09J2463/008—Presence of epoxy resin in the pretreated surface to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane

Definitions

  • the present invention relates to the field of pretreatment of plastic matrix-containing fiber material compositions for bonding, especially in vehicle construction.
  • pre-treatment methods such as primers or physicochemical methods such as plasma pretreatment to improve adhesion of adhesives and sealants has long been known. It has been found that the adhesion of adhesives and sealants on some substrates is very difficult to achieve.
  • Plastic matrix-containing fiber material compositions are such a substrate which is known to be difficult to bond. Especially difficult in this case is the achievement of an early strength when used by means of polyurethane adhesives.
  • DE 102007062529 A1 describes the use of a 2K polyurethane adhesive for bonding metal, plastic or foam substrates or fiber composites.
  • EP 0504681 A1 relates to a process for bonding glass fiber reinforced polyester resin substrates at room temperature without pretreatment using a 2K polyurethane adhesive containing a specific catalyst.
  • WO 03/03/040249 relates to a process for laminating surface films on moldings of polyvinyl chloride, polypropylene, acrylonitrile-butadiene-styrene copolymers, wood or aluminum, which comprises the thermal activation of the film by heating with electromagnetic radiation, the application of a hot melt adhesive to the film surface and joining the film on the molding.
  • the object of the present invention is therefore to provide a pretreatment process which improves the adhesion of polyurethane adhesives to plastic matrix-containing fiber material compositions.
  • the inventive method is characterized by a rapid strength structure (early strength) of the polyurethane composition P , thereby the composite produced using them can be processed or loaded shortly after the application of the polyurethane composition P and the joining of the molding with the substrate, for example by walking , by grinding, by transport or by the removal of fixing brackets. After curing, the composite still has a high strength.
  • the polyurethane composition P is preferably a one-component system or a two-component system.
  • One-component system in this context means a system in which typically a compound is dispensed from a container through a metering tool and in which the compound can perform its function without addition of another compound from a container, for example a minor component, by the metering tool ,
  • two-component system is meant in this context a system which typically consists of a main component and a minor component.
  • the minor component is typically a compound which can react with the major component and result in polymerization of the major component, for example, by initiation or acceleration, and final cure of the major component.
  • polymerization in this document is meant any kind of conversion of low molecular weight compounds (monomers, oligomers, prepolymers) into high molecular weight compounds (polymers, macromolecules, polymers) and includes polyaddition and polycondensation. Therefore, the main component and the minor component are stored in separate containers to prevent a spontaneous reaction of the main component with the minor component.
  • the main component is an adhesive and the minor component is a curing accelerator.
  • the polyurethane composition P is a one-component system comprising a polyurethane polymer P1, wherein the polyurethane polymer P1 is obtainable by the reaction of at least one polyol with at least one polyisocyanate.
  • This reaction can be carried out by reacting the polyol and the polyisocyanate with customary processes, for example at from 50 ° C. to 100 ° C., if appropriate with concomitant use of suitable catalysts, the polyisocyanate being metered in such a way that its isocyanate groups in the Ratio to the hydroxyl groups of the polyol in stoichiometric excess are present.
  • the polyisocyanate is metered so that an NCO / OH ratio of ⁇ 2.5, preferably ⁇ 2.2, is maintained.
  • the NCO / OH ratio here means the ratio of the number of isocyanate groups used to the number of hydroxyl groups used.
  • a content of isocyanate groups of from 0.8 to 2.2% by weight, based on the total weight of the polyurethane polymer P1, remains .
  • Suitable polyols for the preparation of the polyurethane polymer P1 are in particular polyether polyols, polyester polyols and polycarbonate polyols and mixtures of these polyols.
  • Suitable polyether polyols also called polyoxyalkylene polyols or oligoetherols, are in particular those which are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, optionally polymerized with the aid of a starter molecule with two or more active hydrogen atoms such as water, ammonia or compounds with multiple OH or NH groups such as 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and Tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols,
  • Both polyoxyalkylene polyols having a low degree of unsaturation (measured according to ASTM D-2849-69 and expressed in milliequivalents of unsaturation per gram of polyol (mEq / g)) prepared, for example, by means of so-called double metal cyanide complex catalysts (DMC Catalysts), as well as polyoxyalkylene polyols having a higher degree of unsaturation, prepared for example with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides.
  • DMC Catalysts double metal cyanide complex catalysts
  • polyoxyethylene polyols and polyoxypropylene polyols are particularly suitable, in particular polyoxyethylene diols, polyoxypropylene diols, polyoxyethylene triols and polyoxypropylene triols.
  • polyoxyalkylenediols or polyoxyalkylenetriols having a degree of unsaturation lower than 0.02 meq / g and having a molecular weight in the range from 1000 to 30 000 g / mol
  • polyoxyethylenediols Polyoxyethylene triols
  • polyoxypropylene diols and Polyoxypropylentriole having a molecular weight of 400 to 20,000 g / mol.
  • ethylene oxide terminated (“EO endcapped", ethylene oxide endcapped) polyoxypropylene polyols.
  • the latter are specific polyoxypropylene polyoxyethylene polyols obtained, for example, by further alkoxylating pure polyoxypropylene polyols, especially polyoxypropylene diols and triols, upon completion of the polypropoxylation reaction with ethylene oxide, thereby having primary hydroxyl groups.
  • Preferred in this case are polyoxypropylene polyoxyethylene diols and polyoxypropylene polyoxyethylene triols.
  • styrene-acrylonitrile-grafted polyether polyols as are commercially available, for example, under the trade name Lupranol® from Elastogran GmbH, Germany.
  • Suitable polyester polyols are in particular polyesters which carry at least two hydroxyl groups and are prepared by known processes, in particular the polycondensation of hydroxycarboxylic acids or the polycondensation of aliphatic and / or aromatic polycarboxylic acids with dihydric or polyhydric alcohols.
  • polyester polyols which are prepared from dihydric to trihydric alcohols, for example 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Neopentyl glycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the abovementioned alcohols with organic dicarboxylic acids or their anhydrides or esters such as succinic acid, glutaric acid, adipic acid, trimethyladipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, dimer fatty acid, phthalic acid, Phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, hexahydrophthalic acid, trimellitic acid and trimelli
  • polyester diols especially those which are prepared from adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, Dimer fatty acid, phthalic acid, isophthalic acid and terephthalic acid as dicarboxylic acid or from lactones such as ⁇ -caprolactone and from ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, dimer fatty acid diol and 1,4-cyclohexanedimethanol as a dihydric alcohol.
  • Suitable polycarbonate polyols are, in particular, those which are obtainable by reacting, for example, the abovementioned alcohols used for the synthesis of the polyester polyols with dialkyl carbonates, such as dimethyl carbonate, diaryl carbonates, such as diphenyl carbonate or phosgene.
  • dialkyl carbonates such as dimethyl carbonate, diaryl carbonates, such as diphenyl carbonate or phosgene.
  • Particularly suitable are polycarbonate diols, in particular amorphous polycarbonate diols.
  • polystyrene resins are poly (meth) acrylate polyols.
  • These stated polyols preferably have an average molecular weight of from 250 to 30,000 g / mol, in particular from 1,000 to 30,000 g / mol, and an average OH functionality in the range from 1.6 to 3.
  • Particularly suitable polyols are polyester polyols and polyether polyols, especially polyoxyethylene polyol, polyoxypropylene polyol and polyoxypropylene polyoxyethylene polyol, preferably polyoxyethylene diol, polyoxypropylene diol, polyoxyethylene triol, polyoxypropylene triol, polyoxypropylene polyoxyethylene diol and polyoxypropylene polyoxyethylene triol.
  • the polyurethane composition P is a one-component system comprising a polyurethane polymer P1
  • the polyurethane composition P may have, in addition to the other constituents already mentioned, as known to one skilled in the art from one-component polyurethane chemistry.
  • additional constituents for example, solvents, plasticizers and / or extenders extenders, such as Russian, chalk or talc, adhesion promoter, in particular Trialkoxysilanes, and thixotropic agents, such as amorphous silicas, zeolites used.
  • the polyurethane composition P is a two-component polyurethane composition P2 consisting of a polyol component K1 and a polyisocyanate component K2.
  • the polyol component K1 in this case comprises at least one polyol, as described above as suitable polyols for the preparation of the polyurethane polymer P1 , in particular polyether polyols, polyester polyols and polycarbonate polyols and mixtures of these polyols.
  • the polyol component K1 may comprise other constituents.
  • Curing catalysts are advantageously used. Such catalysts are known to those skilled in the reaction of polyisocyanates with polyols, optionally also with polyamines or water. Examples of such catalysts are tin, zinc and bismuth organic metal catalysts, for example dibutyltin dilaurate, or tertiary amines, for example 1,4-diazobicyclo [2.2.2] octane (DABCO) mentioned.
  • DABCO 1,4-diazobicyclo [2.2.2] octane
  • additional constituents may furthermore be diols, in particular polyoxyalkylene diols, and / or diamines.
  • Particularly suitable amines are aliphatic, araliphatic, cycloaliphatic and toxicologically acceptable aromatic amines.
  • the polyisocyanate component K2 comprises at least one polyisocyanate B1.
  • polyisocyanates B1 are, on the one hand, polyisocyanates B1 ', as described above as suitable polyisocyanates for the preparation of the polyurethane polymer P1 .
  • polyisocyanate B1 particularly suitable as polyisocyanate B1 are polyurethane prepolymers B1 " which have at least two isocyanate groups and which are obtained from a reaction of at least one polyisocyanate having a molecular weight of less than 300 g / mol, in particular between 150 g / mol and 270 g / mole, are formed with at least one polyol AB1.
  • polyol AB1 are particularly suitable polyols which are selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, polyols formed from unsaturated monomers and mixtures thereof.
  • polyols are preferably polyols, as described above as suitable polyols for the preparation of the polyurethane polymer P1 , in particular polyether polyols, polyester polyols and polycarbonate polyols and mixtures of these polyols.
  • isocyanate group-containing polyurethane prepolymer is carried out in a known manner and is typically in the stoichiometric excess of the polyisocyanate over the polyol.
  • Particularly suitable polyisocyanates used for this purpose are 2,4- and 2,6-toluene diisocyanate (TDI), 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI) and also mixtures of isomers thereof and mixtures thereof , Particularly preferred is MDI.
  • polyols AB1 preferably have an average molecular weight of from 250 to 30,000 g / mol, in particular from 1,000 to 8,000 g / mol, and are preferably diols or triols, in particular with an average OH functionality in the range of 1.6 to 3.
  • a mixture of polyols AB1 is used which is a mixture of diols and triols.
  • the polyisocyanate component K2 comprises at least one polyisocyanate B1 ' and at least one polyisocyanate polyurethane prepolymer B1 ".
  • Both components K1 and K2 can, in addition to the other components already mentioned, as they know the person skilled in the two-component polyurethane chemistry, have. These can be present in only one component or in both.
  • additional constituents for example, solvents, plasticizers and / or extender fillers, such as Russian, chalks or talc, adhesion promoters, in particular trialkoxysilanes, and thixotropic agents, such as amorphous silicas, zeolites are used.
  • the components K1 and K2 are advantageously formulated such that the volume ratio of component K1 and K2 is between 1: 3 and 3: 1, in particular between 1: 2 and 2: 1. This ratio is particularly preferably about 1: 1.
  • the mixing ratio is preferably such that the NCO groups of component K2 are stoichiometric to the NCO-reactive groups, typically OH groups, of component K1 . If the mixture is not substantially stoichiometric, ie with deviations of more than 5%, the reaction of the components K1 and K2 does not take place optimally, which leads to a reduction in the mechanical properties of the cured polyurethane composition. This is especially true for an excess of the polyol component.
  • the components K1 and K2 are stored separately from each other before use and mixed together only at or just before use.
  • the components are advantageously present in a package consisting of two separate chambers, such that the polyol component K1 is present in one chamber and the polyisocyanate component K2 in the other chamber.
  • the components K1 and K2 are filled into the chambers of the packaging and sealed air and moisture-tight.
  • the polyurethane composition P further comprises at least one filler, wherein the proportion of filler is 20 to 60 wt .-%, in particular 30 to 60 wt .-%, based on the total weight of the composition. It is quite possible and may even be advantageous to use a mixture of different fillers.
  • Suitable fillers are inorganic and organic fillers, for example natural, ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearates, barium sulfate (BaSO 4 , also called barite or barite), calcined kaolins, aluminum oxides, aluminum hydroxides, silicic acids, in particular highly dispersed silicas from pyrolysis processes, Russian, in particular industrially produced carbon black (hereinafter referred to as "carbon black”), PVC powder or hollow spheres.
  • fatty acids in particular stearates, barium sulfate (BaSO 4 , also called barite or barite)
  • BaSO 4 barium sulfate
  • calcined kaolins aluminum oxides
  • aluminum hydroxides aluminum hydroxides
  • silicic acids in particular highly dispersed silicas from pyrolysis processes
  • Russian in particular industrially produced carbon black (hereinafter referred to as "carbon black”),
  • Preferred fillers are calcium carbonates, calcined kaolins, carbon black, finely divided silicas and flame-retardant fillers, such as hydroxides or hydrates, in particular hydroxides or hydrates of aluminum, preferably aluminum hydroxide.
  • the plastic matrix-containing fiber material compositions KFZ are fiber material compositions which contain a plastic matrix.
  • Suitable fibers of such fiber material compositions are fibers selected from the list consisting of inorganic fibers, in particular glass fibers and mineral fibers; metallic fibers and organic fibers.
  • organic fibers selected from the list consisting of aramid fibers, polyester fibers, nylon fibers, Plexiglas fibers, fibers of a homo- or copolymers of ethylene and / or propylene. Most preferably, these are carbon fibers.
  • carbon fibers also referred to as carbon fibers or carbon fibers
  • carbon fibers means industrially produced fibers from carbonaceous starting materials, which are converted by pyrolysis into graphitic carbon.
  • the fibers may here be short fibers or long fibers, spun, woven or non-woven fibers or filaments. Furthermore, the fibers may be directional or stretched fibers. Furthermore, it may be advantageous to use different fibers, both in geometry and composition, with each other.
  • the fiber material comprises spaces. These spaces are built up by suitable manufacturing methods. Preferably, the spaces are at least partially open and allow the penetration of the plastic matrix.
  • the body constructed of fibers can be prepared by a variety of methods known to those skilled in the art. In particular, bodies are used, which are a tissue, scrim or knitted fabrics are.
  • the fibrous material is preferably a fabric or a scrim, in particular a multiaxial scrim.
  • Suitable plastic matrices are selected from the list consisting of epoxy resin, unsaturated polyester resin, vinyl ester resin, phenol-formaldehyde resin, diallyl phthalate resin, (meth) acrylate resin, polyurethane, amino resin, melamine resin and urea resin.
  • Particularly preferred as the plastic matrix is epoxy resin. It is therefore advantageous if the plastic matrix-containing fibrous composition KFZ is a plastic matrix comprising at least one epoxy resin.
  • Fittings of plastic matrix containing fiber material compositions car be prepared for example by webs of fibrous material are layered on a mold cavity surface defining the shape of the desired molded article.
  • the layered webs of fiber material are impregnated with non-cured, liquid plastic material and impregnated.
  • the liquid is uncured precursor material for the plastic material which will form a solid matrix around the fibers of the fiber material.
  • the impregnation with the liquid plastic material may be accomplished before or after the layered webs are disposed in the mold. There, the layers are compacted to a desired shape and the liquid plastic material is heated and cured to a solid matrix.
  • the cured products, ie the shaped bodies of plastic matrix-containing fiber material compositions of the motor vehicle are preferably lightweight and very strong.
  • Preferred plastic matrix-containing fiber material compositions KFZ are produced on the basis of glass fibers and / or carbon fibers in a polyester or epoxy matrix. Such compositions can be prepared by various processes in a known manner from a polyester or polyepoxide and glass fibers and / or carbon fibers.
  • the plastic matrix-containing pulp compositions KFZ is a material whose plastic matrix contains epoxy resin and whose fiber material comprises carbon fibers.
  • step a) IR radiation is applied to a defined region DB of the shaped part made of motor vehicle .
  • fitting is meant an article having a three-dimensional extension.
  • it is shaped pieces with a rather planar shape, for example, parts of the casing of vehicles.
  • it is molded parts, such as those used in vehicle construction, aircraft, boat building or other mechanically highly stressed components.
  • Step a) takes place before step b).
  • step a) the application of IR radiation is carried out on the remote surface of the defined region DB on which the polyurethane composition P is applied in step b).
  • step b) the fitting, for example, a fitting with a rather planar shape, so it may be advantageous for improving the adhesion of the polyurethane composition P on the molding, if in step a) the application of the IR radiation on one side of the defined region DB of the molding of motor vehicle is performed and in step b) the polyurethane composition P. the other side of the defined area DB, so the opposite side, is applied.
  • IR radiation is thus applied, for example, to the back or rear side of the molding area DB and the polyurethane composition P is applied to the front side thereof.
  • the IR radiation in step a) is preferably IR radiation having a wavelength of 0.78 ⁇ m-50 ⁇ m, preferably 1.4 ⁇ m-10 ⁇ m, particularly preferably 2 ⁇ m-3 ⁇ m.
  • a cleaning of the defined region DB of the shaped part from motor vehicle occurs, in particular a cleaning with solvents.
  • the region DB of the shaped part of motor vehicle cools off after step a).
  • the surface temperature of the defined region DB of the molding made of motor vehicle is ⁇ 30 ° C, in particular 20-30 ° C. More preferably, between the steps a) and b) corresponds to the surface temperature of the defined range DB of the molding of motor vehicle of the ambient temperature.
  • steps a) and b) there is a time period of 2 to 200 minutes, in particular 5 to 180 minutes, particularly preferably 5 to 120 minutes.
  • Suitable substrates are in particular substrates which are selected from the group consisting of concrete, mortar, brick, brick, gypsum, a Natural stone such as granite or marble, glass, glass ceramic, metal or metal alloy, wood, plastic or lacquer.
  • a particularly preferred substrate to be bonded is a molded part based on glass fibers and / or carbon fibers in a polyester or epoxy matrix.
  • the substrate in step c) is a shaped part made of motor vehicle, in particular a material whose plastic matrix contains epoxy resin and whose fiber material comprises carbon fibers.
  • the inventive method comprises a step d) curing the polyurethane compositions P.
  • the cure of the polyurethane compositions P is determined primarily by the manner in which the composition comes into contact with moisture or water.
  • the moisture required for the curing can either originate from the air (atmospheric moisture) or it can be mixed, for example, as an aqueous paste of the composition.
  • the polyurethane compositions P are cured , at least in part, by the introduction of heat, the temperature of the composition being at least 50.degree. C. during the exposure to heat, and advantageously between 60.degree. C. and 160.degree. C., preferably between 80.degree. C. and 140.degree. particularly preferably between 90 ° C and 130 ° C, is located.
  • the heat necessary for heat curing the composition can be generated with any source of energy. Suitable means for heating are in particular circulating air ovens, hot air blower or infrared radiator. If at least one of the components is ferromagnetic and / or the composition is a piezoelectric, ferromagnetic or contains superparamagnetic material, the heating can also be done by applying magnetic and / or alternating electric fields, in particular microwaves or induction; this allows a particularly rapid heating of the compositions described.
  • component K2 dried chalk was added to the polyisocyanate and incorporated with stirring and under vacuum homogeneously at 25 ° C in a Vakuumdissolver for 20 minutes. Subsequently, this polyisocyanate component K2 was filled into the second chamber of the above-mentioned side-by-side double cartridge and also closed air-tight and moisture-tight with plastic piston.
  • Components K1 and K2 were mixed in the amount indicated in Table 1 by means of static mixer volumetrically 1: 1.
  • Component K2 (Wt .-%) Desmodur® VH 20 48.0 chalk 52.0
  • ZSF Tensile shear strength
  • the test specimens of Examples 1-10 were made from the above-described adhesive composition and two sheets of plastic matrix-containing pulp composition, whose plastic matrix contains epoxy resin and whose fiber material comprises carbon fibers ( EK ), each measuring 100 x 45 x 1.5 mm the bond area was 15 x 45 mm with a layer thickness of 1.6 mm.
  • the adherend surface of the EK was first wiped off once with a cloth soaked in a solvent listed in Table 2 (cleaning).
  • the surface facing away from the surface to be bonded was subsequently heated for 60 sec to a temperature of 140 ° C by means of an IR radiator (company Vulkan, Switzerland, wavelength of the IR radiation 2.5 microns, 1650 watts).
  • IR radiator company Vulkan, Switzerland, wavelength of the IR radiation 2.5 microns, 1650 watts
  • Comparative Example 5 the surface to be bonded was pretreated by 3M Scotch-Brite nonwoven.
  • the adhesive was applied to one of the surfaces to be bonded and the EK was added . Subsequently, the adhesive was cured by heating through the aforementioned IR radiator at 140 ° C for 60 seconds. Before the adhesive was applied to the surface to be bonded, the surface temperature of the surface to be bonded corresponded to the room temperature.
  • the pulling speed was 20mm / min.
  • the tensile shear strength was determined to be 2 minutes, respectively 7 days (storage at 23 ° C for 7 days) after curing of the adhesive.
  • the results of these tensile shear tests are summarized in Table 2.
  • the measured values in MPa are mean values from 3 independent tests.
  • the fracture pattern was divided into adhesive fracture pattern or cohesive fracture pattern by eye after the tensile shear test using adhesive remaining on the EK .
  • Table 2. Tensile shear test and sample preparation; BB: fracture image, ad: adhesive fracture pattern, ko: cohesive fracture pattern No. Cleaning with solvent IR pretreatment. Time (60 sec at 140 ° C) other pretreatment. Time [min] between IR pre-treatment.
  • BB ZSF [MPa] after 2 min BB ZSF [MPa] after 7 d
  • BB 1 isopropanol No - - 0.6, ad 10.0, ko 2 n-heptane No - - 0.2, ad 5.9, ad 3 acetone No - - 0.3, ad n / A 4 isopropanol No plasma - 0.1, ad 3.6, ad 5 isopropanol No Scotch-Brite fleece, 3M - 0.5, ad 6.8, ad 6 isopropanol Yes - 5 1.6, ko 10.9, ko.
  • Examples 6-10 which were pretreated with IR radiation, have an improved tensile shear strength compared to Comparative Examples 1-5, both shortly after curing (early strength) and 7 days afterwards. Further, Examples 6-9 have a cohesive fracture pattern.
  • Examples 6 and 7 which have a time interval of 5 minutes, respectively 30 minutes, between IR pretreatment and application of the adhesive, have a better early strength compared to Examples 8 to 10, their time 60 min, 120 min , respectively 180 min.
  • ZSF Tensile shear strength
  • test specimens of Examples 11-18 were prepared from the adhesive composition described above and two sheets of plastic matrix-containing pulp composition whose plastic matrix contains epoxy resin and its fiber material Carbon fibers ( EK ), each with the dimensions 100 x 45 x 1.5 mm produced, while the adhesive surface was 15 x 45 mm with a layer thickness of 1.6 mm.
  • the EK come from different manufacturers (manufacturers 1 - 4)
  • the surface of the EK to be bonded was first wiped off once with a cloth soaked in isopropanol (cleaning).
  • the surface facing away from the surface to be bonded was then heated for 60 seconds to a temperature of 140 ° C. by means of an IR radiator (Vulkan, Switzerland, wavelength of the IR radiation 2.5 ⁇ m, 1650 watts ).
  • IR radiator Vulkan, Switzerland, wavelength of the IR radiation 2.5 ⁇ m, 1650 watts
  • the adhesive was applied to one of the surfaces to be bonded and the EK joined.
  • the surface temperature of the surface to be bonded corresponded to the room temperature.
  • the adhesive was cured by heating by means of the above-mentioned IR emitter to 140 ° C for 60 seconds. The pulling speed was 20mm / min. The tensile shear strength was determined 1 minute after the end of curing of the adhesive.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Claims (10)

  1. Procédé de collage de pièces moulées constituées de compositions de matière fibreuse contenant une matrice en plastique KFZ avec des compositions de polyuréthane P, comprenant les étapes suivantes :
    a) l'application d'un rayonnement IR sur une zone définie DB de la pièce moulée constituée de FKZ ou l'application d'un rayonnement IR sur la surface opposée de la zone définie DB sur laquelle la composition de polyuréthane P est appliquée à l'étape b ;
    b) l'application d'une composition de polyuréthane P sur la zone définie DB de la pièce moulée constituée de KFZ ;
    c) l'assemblage de la composition de polyuréthane P sur la zone définie DB de la pièce moulée constituée de KFZ avec un substrat,
    d) le durcissement de la composition de polyuréthane P.
  2. Procédé selon la revendication 1, caractérisé en ce que les compositions de matière fibreuse contenant une matrice en plastique KFZ consistent en une matrice en plastique comprenant au moins une résine époxyde.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la matière fibreuse des compositions de matière fibreuse contenant une matrice en plastique KFZ consiste en des fibres organiques.
  4. Procédé selon la revendication 1 ou 2, caractérisé en ce que la matière fibreuse des compositions de matière fibreuse contenant une matrice en plastique KFZ consiste en des fibres de carbone.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'à l'étape a), la température de surface de la zone définie DB de la pièce moulée constituée de KFZ est portée pendant 5 à 600 s, notamment pendant 30 à 180 s, à une température de 60 à 200 °C, notamment de 120 à 160 °C.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'un nettoyage de la zone définie DB de la pièce moulée constituée de KFZ a lieu temporellement avant l'étape a), notamment avec des solvants.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'entre les étapes a) et b), la température de surface de la zone définie DB de la pièce moulée constituée de KFZ est ≤ 30 °C.
  8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il y a une durée de 2 à 200 minutes, notamment de 5 à 180 minutes, de manière particulièrement préférée de 5 à 120 minutes, entre les étapes a) et b).
  9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le substrat à l'étape c) est une pièce moulée constituée de KFZ.
  10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les compositions de matière fibreuse contenant une matrice en plastique KFZ consistent en un matériau dont la matrice en plastique contient une résine époxyde et dont la matière fibreuse comprend des fibres de carbone.
EP12735288.8A 2011-07-12 2012-07-11 Procédé de prétraitement de pièces de formage constituées de compositions de matière fibreuse contenant une matrice en matière synthétique et destinées au collage Not-in-force EP2732001B1 (fr)

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EP12735288.8A EP2732001B1 (fr) 2011-07-12 2012-07-11 Procédé de prétraitement de pièces de formage constituées de compositions de matière fibreuse contenant une matrice en matière synthétique et destinées au collage

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EP11173608A EP2546314A1 (fr) 2011-07-12 2011-07-12 Procédé de prétraitement de pièces de formage constituées de compositions de matière fibreuse contenant une matrice en matière synthétique et destinées au collage
PCT/EP2012/063587 WO2013007751A1 (fr) 2011-07-12 2012-07-11 Procédé de prétraitement à des fins de collage de pièces moulées constituées de compositions fibreuses contenant une matrice plastique
EP12735288.8A EP2732001B1 (fr) 2011-07-12 2012-07-11 Procédé de prétraitement de pièces de formage constituées de compositions de matière fibreuse contenant une matrice en matière synthétique et destinées au collage

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EP2732001A1 EP2732001A1 (fr) 2014-05-21
EP2732001B1 true EP2732001B1 (fr) 2018-03-07

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EP12735288.8A Not-in-force EP2732001B1 (fr) 2011-07-12 2012-07-11 Procédé de prétraitement de pièces de formage constituées de compositions de matière fibreuse contenant une matrice en matière synthétique et destinées au collage

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EP (2) EP2546314A1 (fr)
JP (1) JP5972973B2 (fr)
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KR101581636B1 (ko) * 2015-05-19 2015-12-30 한규복 비금속광물 착색용 조성물 및 이를 이용한 착색된 비금속 광물의 제조방법
EP3994193A1 (fr) * 2019-07-02 2022-05-11 Sika Technology AG Composition de polyuréthane à deux constituants pour la production à grande échelle de modèles et d'outils par impression 3d

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US4659412A (en) * 1984-10-22 1987-04-21 The Dow Chemical Company Method for adhering a coating material to densified random-fiber composite sheet
DE3916874A1 (de) * 1989-05-24 1990-11-29 Basf Ag Weiche, elastische polyurethan-folien, verfahren zu ihrer herstellung und ihre verwendung
DE4108877A1 (de) 1991-03-19 1992-09-24 Bayer Ag Verfahren zur verklebung von substraten aus glasfaserverstaerktem polyesterharz
DE4432271A1 (de) * 1994-09-09 1996-03-14 Teroson Gmbh Verfahren zum Verbinden von Kunststoff-Formteilen
JP3595403B2 (ja) * 1996-02-15 2004-12-02 株式会社ブリヂストン ゴム・金属接着複合体の製造方法
JP4444489B2 (ja) * 2000-12-15 2010-03-31 帝人化成株式会社 成形品の構造補強方法および構造補強成形品
JP2003027012A (ja) * 2001-07-23 2003-01-29 Hitachi Chem Co Ltd 繊維強化プラスチック成形品の接着方法及びその接着物
DE10201190A1 (de) 2002-01-14 2003-07-31 Henkel Kgaa Thermische Aktivierung von Folien
DE102007062529A1 (de) * 2007-12-20 2009-06-25 Henkel Ag & Co. Kgaa 2K-PU-Klebstoff zum Verkleben von Faserformteilen

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CN103649252A (zh) 2014-03-19
CN103649252B (zh) 2016-04-20
US9028640B2 (en) 2015-05-12
JP5972973B2 (ja) 2016-08-17
JP2014527922A (ja) 2014-10-23
EP2546314A1 (fr) 2013-01-16
EP2732001A1 (fr) 2014-05-21
WO2013007751A1 (fr) 2013-01-17
US20140124135A1 (en) 2014-05-08

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